Ruthenium dihydrogen complex for C-H activation: Catalytic H/D exchange under mild conditions

Martin H.G. Prechtl; Markus Hölscher; Yehoshoa Ben-David; Nils Theyssen; David Milstein; Walter Leitner

doi:10.1002/ejic.200800359

Ruthenium dihydrogen complex for C-H activation: Catalytic H/D exchange under mild conditions

Martin H.G. Prechtl, Markus Hölscher, Yehoshoa Ben-David, Nils Theyssen, David Milstein, Walter Leitner

Weizmann Institute of Science, Israel

Research output: Contribution to journal › Article › peer-review

36 Citations (Scopus)

Abstract

Catalytic H/D-exchange reactions were studied with [Ru(dtbpmp) (η²-H₂)(H)₂] (1) as catalyst. Under mild reaction conditions (25-75°C) a wide range of arenes and olefins undergo H/D exchange with [D₆]benzene. A preference for protons at sp ² carbons was observed with conversions up to >90% and significant regioselectivity in certain cases. For more reaction insights NMR-based kinetic studies were performed with naphthalene as substrate, revealing an activation energy of 15.8 kcal mol^-1 for the H/D exchange at the β-position. Furthermore, the key steps of the reaction mechanism were investigated by means of DFT calculations for both model complexes (PMe ₂ donor sites) and real catalysts (PtBu₂ donor sites). The calculations resulted in Gibb's free activation energies in the range of 10-16 kcal mol^-1, indicating H/D exchange at the β-position of naphthalene to be clearly favoured over the α-position, which is in full accordance with the experimental observations.

Original language	English
Pages (from-to)	3493-3500
Number of pages	8
Journal	European Journal of Inorganic Chemistry
Issue number	22
DOIs	https://doi.org/10.1002/ejic.200800359
Publication status	Published - Aug 2008

Keywords

CH activation
DFT calculations
Deuteration
H/D exchange
Ruthenium dihydrogen complexes

ASJC Scopus subject areas

Inorganic Chemistry

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title = "Ruthenium dihydrogen complex for C-H activation: Catalytic H/D exchange under mild conditions",

abstract = "Catalytic H/D-exchange reactions were studied with [Ru(dtbpmp) (η2-H2)(H)2] (1) as catalyst. Under mild reaction conditions (25-75°C) a wide range of arenes and olefins undergo H/D exchange with [D6]benzene. A preference for protons at sp 2 carbons was observed with conversions up to >90% and significant regioselectivity in certain cases. For more reaction insights NMR-based kinetic studies were performed with naphthalene as substrate, revealing an activation energy of 15.8 kcal mol-1 for the H/D exchange at the β-position. Furthermore, the key steps of the reaction mechanism were investigated by means of DFT calculations for both model complexes (PMe 2 donor sites) and real catalysts (PtBu2 donor sites). The calculations resulted in Gibb's free activation energies in the range of 10-16 kcal mol-1, indicating H/D exchange at the β-position of naphthalene to be clearly favoured over the α-position, which is in full accordance with the experimental observations.",

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year = "2008",

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AU - Prechtl, Martin H.G.

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AU - Ben-David, Yehoshoa

AU - Theyssen, Nils

AU - Milstein, David

AU - Leitner, Walter

PY - 2008/8

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N2 - Catalytic H/D-exchange reactions were studied with [Ru(dtbpmp) (η2-H2)(H)2] (1) as catalyst. Under mild reaction conditions (25-75°C) a wide range of arenes and olefins undergo H/D exchange with [D6]benzene. A preference for protons at sp 2 carbons was observed with conversions up to >90% and significant regioselectivity in certain cases. For more reaction insights NMR-based kinetic studies were performed with naphthalene as substrate, revealing an activation energy of 15.8 kcal mol-1 for the H/D exchange at the β-position. Furthermore, the key steps of the reaction mechanism were investigated by means of DFT calculations for both model complexes (PMe 2 donor sites) and real catalysts (PtBu2 donor sites). The calculations resulted in Gibb's free activation energies in the range of 10-16 kcal mol-1, indicating H/D exchange at the β-position of naphthalene to be clearly favoured over the α-position, which is in full accordance with the experimental observations.

AB - Catalytic H/D-exchange reactions were studied with [Ru(dtbpmp) (η2-H2)(H)2] (1) as catalyst. Under mild reaction conditions (25-75°C) a wide range of arenes and olefins undergo H/D exchange with [D6]benzene. A preference for protons at sp 2 carbons was observed with conversions up to >90% and significant regioselectivity in certain cases. For more reaction insights NMR-based kinetic studies were performed with naphthalene as substrate, revealing an activation energy of 15.8 kcal mol-1 for the H/D exchange at the β-position. Furthermore, the key steps of the reaction mechanism were investigated by means of DFT calculations for both model complexes (PMe 2 donor sites) and real catalysts (PtBu2 donor sites). The calculations resulted in Gibb's free activation energies in the range of 10-16 kcal mol-1, indicating H/D exchange at the β-position of naphthalene to be clearly favoured over the α-position, which is in full accordance with the experimental observations.

KW - CH activation

KW - DFT calculations

KW - Deuteration

KW - H/D exchange

KW - Ruthenium dihydrogen complexes

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Ruthenium dihydrogen complex for C-H activation: Catalytic H/D exchange under mild conditions

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